The development of mesoporous materials has led to their use in a wide variety of chemical applications over the past several years. For example, mesoporous materials have been used on an industrial scale in catalytic cracking operations and other chemical processes. Despite these and other successful applications, the breadth of these applications has still been limited due to the fabrication techniques and the nature of the species commonly used to fabricate these materials. The fabrication techniques that have enabled the development of these high surface area materials (hydrolysis and condensation chemistry) have proven to be best suited for the preparation of nanostructured ceramic oxides. While ceramic oxide mesoporous materials have proven useful in a wide variety of applications, their usefulness does not cover the full range of potentially beneficial applications of mesoporous materials.
For example, in applications such as drug delivery, the relative insolubility of mesoporous silica can hamper the usefulness of the material where dissolution is desired. In contrast, due both to its ability to dissolve in a controlled manner in situ, and the ability of natural, biological processes to put the dissolved material to productive use, a mesoporous carbonate material has great potential as a next generation drug delivery system. Mesoporous carbonate materials could be used, for example, as a resorbable filler material during bone surgery, wherein the interior pores of the material are impregnated with analgesics, antibiotics, or other pharmaceuticals. The intraporous species could be released over time, as the carbonate material is dissolved by the body, affording a time released delivery. Other potential applications for mesoporous carbonate materials, which simultaneously take advantage of the geometrical properties of mesoporous materials and the physical and chemical properties of carbonates, include chemical and catalytic applications, and as negative substrates for forming other mesoporous structures. Thus, there exists a need for a method for fabricating mesoporous carbonate materials.
Accordingly, it is an object of the present invention to provide mesoporous carbonate materials and a method for making the same. As used herein, xe2x80x9cmesoporousxe2x80x9d refers to materials that have a high surface area as a result of pores covering the surface of the materials. As further used herein, xe2x80x9cmesoporousxe2x80x9d generally refers to materials wherein these pores are generally between about 1 nanometer and about 15 nanometers, but should also be interpreted to include materials wherein these pores range from between about 1 nanometer up to about 100 nanometers.
The method for making mesoporous carbonate materials of the present invention involves first providing a solution containing a non-ionic surfactant and a metal salt having an organic counter ion. Carbon dioxide is reacted with the solution to form the metal carbonate structure, but prior to the addition of the carbon dioxide, a sufficient amount of base is added to react with the acidic byproducts that are formed by the addition of carbon dioxide. In this manner, the reaction is prevented from reversing as the metal carbonate structure is formed. Suitable bases include, but are not limited to, NH4OH
In general, any non-ionic surfactant that will form a microemulsion in water and carbon dioxide is suitable for the method of the present invention. While not meant to be limiting, polyethyleneglycol was used as the surfactant in the preferred embodiment of the present invention set forth herein. Similarly, while the preferred embodiment of the present invention described herein utilized calcium and magnesium, other metals may be used in the practice of the present invention include the alkaline earth metals (Be, Mg, Ca, Sr, Ba, and Ra), transition metals such as Ni, Ti, and Zn, and alkali metals such as Li.
The mesoporous carbonate materials made by the method of the present invention may further be cleaned with a solvent, such as supercritical carbon dioxide (SCCO2). Preferred solvents should be capable of extracting the surfactant and resultant organic salt from the mesoporous carbonate product material. Thus, the use of both non-ionic surfactants and salts having an organic counter ion allows a single solvent, such as SCCO2, to perform the entire extraction in a single, elegant step.
The present invention allows the use of any organic counter ion. In the preferred embodiment described herein, the metal salt of calcium acetate was selected and acetate thus formed the organic counter ion. As indicated above, the selection of acetate as the organic counter ion was merely to facilitate the extraction of the reaction product with supercritical CO2, and the invention should be broadly construed to contemplate the use of any organic counter ion, provided it is soluble in the solvent selected for extraction, as acceptable for practicing this aspect of the present invention.
Supercritical carbon dioxide (SCCO2) may fill both the role of a reactant and as a solvent for cleaning the final product. However, while some form of carbon dioxide is necessary to form the mesoporous carbonate structures, alternative solvents may be used in substitution for SCCO2. Nevertheless, due to the convenience of using SCCO2 as both a precursor to form the mesoporous carbonate structures and as a solvent for the extraction of the final product, SCCO2 is the preferred solvent.